JP2008122667A - Photosensitive resin composition and semiconductor device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive resin composition provided with excellent photosensitive characteristic and a semiconductor device. <P>SOLUTION: The photosensitive resin composition comprises a resin component (A) of which the alkali solubility changes under the action of acid, a photoreactive compound (B) which generates the above acid by a photoreaction, and a solvent (C), wherein a heat resistant resin compound comprising a polyimide precursor or polybenzoxazole precursor having an asymmetric carbon site represented by a general formula (1) is used as the resin component (A), wherein X<SB>1</SB>is a divalent to tetravalent organic group; Y<SB>1</SB>is a divalent to hexavalent organic group; p and q are each 0 or an integer of 1-4; R<SB>1</SB>is a hydrogen atom or a 1-20C organic group; l and m are each 0 or an integer of 1-2; and n is an integer of 2-1,000, provided that R<SB>1</SB>is hydrogen or a monovalent organic group. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a photosensitive resin composition having excellent insulating properties and mechanical characteristics and excellent photosensitive characteristics, and a semiconductor device using the photosensitive resin composition.

  As is well known, an inorganic material has been conventionally used as an insulating material used for an interlayer insulating layer in a semiconductor device. In recent years, instead of such inorganic materials, organic materials having excellent heat resistance such as polyimide resins have been used taking advantage of their properties.

  For example, in the manufacture of a semiconductor integrated circuit, first, a semiconductor substrate is covered with a protective film such as a silicon oxide film except for a predetermined portion of the circuit element, and a first conductor layer is formed on the exposed circuit element. An interlayer insulating film layer is formed on the semiconductor substrate, and then a photosensitive resin film is formed on the interlayer insulating film layer so that a predetermined portion of the interlayer insulating film layer is exposed to the photosensitive resin film. Windows are provided. The interlayer insulating film layer in the window portion is selectively etched by a dry etching means using a gas such as oxygen or carbon tetrafluoride to form a hole. The photosensitive resin layer is completely removed using an etching solution that corrodes only the photosensitive resin layer without corroding the first conductor layer exposed from the hole. Furthermore, a second conductor layer is formed on the interlayer insulating layer, and electrical connection with the first conductor layer is performed through the hole. Furthermore, when forming a multilayer wiring structure having three or more layers, the above steps are repeated to form each layer.

  In the manufacture of semiconductor integrated circuits based on such a wide variety of processes and the use of various materials, it is required to reduce the manufacturing cost. As one of the means for solving the problem, a pattern by exposure and development is required. It has been desired to develop a heat-resistant photosensitive resin material that can be used by leaving a part of the resist necessary for development after formation as an insulating material.

  Recently, in order to shorten the semiconductor manufacturing process, photosensitive polyimide, polybenzoic acid, which can easily form a patterned cured film by coating, exposing, and developing, can be used to shorten the semiconductor manufacturing process. Oxazole is becoming the mainstream as an insulating material for semiconductor devices. As a conventional photosensitive polyimide, a negative type which uses an organic solvent as a developer and insolubilizes an exposed portion is mainly used. For example, a method of adding or mixing a compound having a photosensitive group to an acid functional group of a polyimide precursor The photosensitive polyimide obtained by (patent document 1) etc. is proposed as a negative photosensitive polyimide which produces contrast by photocrosslinking reaction.

  On the other hand, recently, there has been an increasing demand for alkaline aqueous solution development from the viewpoint of material cost and environmental conservation. As such an alkali development type photosensitive resin material, a material using a naphthoquinonediazide compound as a photosensitizer and a polybenzoxazole precursor having an acid functional group as a base resin has been proposed (Patent Document 2).

JP-A-54-109828 Japanese Examined Patent Publication No. 1-46862

  The photosensitive resin is heat-treated at a high temperature after pattern formation, thereby forming a tough cured film having necessary physical properties. As the characteristics of the cured film, excellent mechanical characteristics and thermal characteristics are required, and high characteristic values are required particularly for semiconductor applications. At present, it is desired to provide a photosensitive resin composition of excellent quality in which such characteristic values are further enhanced.

  The present invention has been made in view of the above-described conventional circumstances, and the subject thereof is a photosensitive resin composition having excellent insulating properties and mechanical characteristics, and excellent photosensitive characteristics, and the photosensitive resin. It is providing the semiconductor device using a composition.

（式中、Ｘ₁は２〜４価の有機基、Ｙ₁は２〜６価の有機基、ｐ、ｑは０または１から４の整数、Ｒ₁は水素原子または炭素数１〜２０の有機基であり、ｌ、ｍは０または１〜２までの整数、ｎは２〜１０００の整数である。ただし、Ｒ₁は水素または１価の有機基である。）で示される繰り返し単位を有するポリイミド前駆体あるいはポリベンゾオキサゾール前駆体、これら２種の前駆体の共重合体、および前記２種の前駆体の混合物から選ばれる少なくとも一種からなる耐熱樹脂であることを特徴とする。 In order to solve the above problems, a photosensitive resin composition according to the present invention comprises a resin component (A), a photoreactive compound (B) that generates an acid by photoreaction, and a solvent (C). A photosensitive resin composition, wherein the resin component (A) has an asymmetric carbon moiety and has the following general formula (1):

(In the formula, X ₁ is a divalent to tetravalent organic group, Y ₁ is a divalent to hexavalent organic group, p and q are 0 or an integer of 1 to 4, and R ₁ is a hydrogen atom or a carbon number of 1 to 20) An organic group, l and m are 0 or an integer from 1 to 2, and n is an integer from 2 to 1000, provided that R ₁ is hydrogen or a monovalent organic group. It is a heat-resistant resin comprising at least one selected from a polyimide precursor or a polybenzoxazole precursor, a copolymer of these two precursors, and a mixture of the two precursors.

  The photoreactive compound (B) is preferably a compound that generates a carboxyl group by photoreaction.

  Moreover, the semiconductor device according to the present invention is characterized in that an insulating portion is formed by the photosensitive resin composition of the present invention.

  According to the present invention, a photosensitive resin composition having excellent insulating characteristics and mechanical characteristics, and having excellent photosensitive characteristics, and excellent insulating characteristics and mechanical characteristics using the photosensitive resin composition as an insulating portion. It has become possible to provide semiconductor devices at low cost.

As described above, the resin composition according to the present invention includes a resin component (A), a photoreactive compound (B) that generates an acid by photoreaction, and a solvent (C). The resin component (A) has an asymmetric carbon moiety and has a repeating unit represented by the general formula (1), a polyimide precursor or a polybenzoxazole precursor, and these two kinds of precursors And a heat-resistant resin comprising at least one selected from the above-mentioned copolymer and a mixture of the two precursors.
Below, each said component is explained in full detail.

(Resin component (A))
In the present invention, the resin component (A) is composed of, for example, a tetracarboxylic dianhydride and / or a dicarboxylic acid and / or a dicarboxylic acid having an acid functional group and a diamine and / or a diamine having an acid functional group. A heat-resistant resin such as a polyimide precursor or polybenzoxazole precursor, a copolymer of these two precursors, or a mixture of the two precursors.

Examples of the compound having a divalent to tetravalent organic group represented by X ₁ in the general formula (1) include a tetracarboxylic dianhydride and / or a general dicarboxylic acid and / or a dicarboxylic acid having an acid functional group. The thing which consists of is mentioned.

  Examples of the tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, and 2,3,3 ′, 4′-biphenyltetracarboxylic acid. Acid dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 2,2 ′, 3,3 ′ -Benzophenone tetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 1,1 -Bis (3,4-dicarboxyphenyl) ethane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, Screw (2,3 Dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, 1,2,3,4-cyclopentanetetra Carboxylic dianhydride, 2,2-bis (4- (4-aminophenoxy) phenyl) propane, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetra Carboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 3,3 ′, 4,4′-tetraphenyl Examples thereof include silanetetracarboxylic dianhydride and 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride. These are used alone or in combination of two or more. In addition, the said tetracarboxylic dianhydride which can be used by this invention is not necessarily limited to what was mentioned here.

  Among the specific candidate compounds for the tetracarboxylic dianhydride, pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′- Biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 2,2 ′, 3 , 3′-benzophenonetetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, N- (Trimellitic dianhydride) -2,2′-bis (3-amino-4-hydroxyphenyl) hexafluoropropane is preferred for obtaining good film properties with high heat resistance.

Examples of the above-mentioned general dicarboxylic acid (having no other acid functional group) which is a compound having a divalent to tetravalent organic group represented by X ₁ in the general formula (1) include, for example, 3- Fluoroisophthalic acid, 2-fluoroisophthalic acid, 3-fluorophthalic acid, 2-fluorophthalic acid, 2,4,5,6-tetrafluoroisophthalic acid, 3,4,5,6-tetrafluorophthalic acid, 4, 4′-hexafluoroisopropylidenediphenyl-1,1′-dicarboxylic acid, perfluorosuberic acid, 2,2′-bis (trifluoromethyl) -4,4′-biphenylenedicarboxylic acid, terephthalic acid, isophthalic acid, 4 , 4′-oxydiphenyl-1,1′-dicarboxylic acid and the like. These are used alone or in combination of two or more. In addition, the said dicarboxylic acid which can be used by this invention is not necessarily limited to what was mentioned here. Of these dicarboxylic acids, terephthalic acid, isophthalic acid, and 4,4′-oxydiphenyl-1,1′-dicarboxylic acid are preferable for obtaining good film properties with high heat resistance.

Moreover, in order to adjust the alkali solubility of the resin composition of this invention as a compound which has a 2-4 tetravalent organic group shown by X < ₁ > in the said General formula (1), the acid functionality which shows alkali solubility. A dicarboxylic acid having a group can be used. Examples of the dicarboxylic acid having an acid functional group include N- (trimellitic dianhydride) -2,2′-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, N- (trimellitic acid). Dianhydride) -2,2'-bis (3-amino-4-hydroxyphenyl) propane, N- (trimellitic dianhydride) -4,4'-diamino-3,3'-dihydroxybiphenyl, N -(Trimellitic dianhydride) -2,2'-bis (3-amino-4-hydroxyphenyl) sulfone, N- (trimellitic dianhydride) -2,2'-bis (3-amino- 4-hydroxyphenyl) ether, N- (trimellitic dianhydride) -2,2'-bis (3-amino-4-hydroxyphenyl) propane, N- (trimellitic dianhydride) -2,4 -Diaminopheno And N- (trimellitic dianhydride) -2,5-diaminophenol, N- (trimellitic dianhydride) -1,4-diamino-2,5-dihydroxybenzene, and the like. These are used alone or in combination of two or more. The dicarboxylic acid having an acid functional group that can be used in the present invention is not necessarily limited to those listed here.

  Among the dicarboxylic acids having an acid functional group, N- (trimellitic dianhydride) -2,2′-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, N- (trimellitic dianhydride Product) -2,2′-bis (3-amino-4-hydroxyphenyl) propane, N- (trimellitic dianhydride) -4,4′-diamino-3,3′-dihydroxybiphenyl, N- ( Trimellitic dianhydride) -2,2′-bis (3-amino-4-hydroxyphenyl) sulfone, N- (trimellitic dianhydride) -2,2′-bis (3-amino-4-) Hydroxyphenyl) ether and N- (trimellitic dianhydride) -2,2′-bis (3-amino-4-hydroxyphenyl) propane are preferred for obtaining good film properties with high heat resistance.

  A heat-resistant resin (resin component (1)) selected from the polyimide precursor or polybenzoxazole precursor having an asymmetric carbon, a copolymer of these two precursors, and a mixture of the two precursors. The asymmetric carbon in A)) can be introduced by using an acid component having an asymmetric carbon moiety. Examples of the acid component having an asymmetric carbon moiety include (R)-(−)-citramalic acid, (S)-(+)-citramalic acid, D-malic acid, (−)-camphoric acid, (+) Camphoric acid, diparatoluoyl-D-tartaric acid, diparatoluoyl-L-tartaric acid, dibenzoyl-D-tartaric acid, dibenzoyl-L-tartaric acid, diparaanisoyl-D-tartaric acid, diparaanisoyl-L-tartaric acid, (R) -spiro- [3,3] -Heptane-2,6-carboxylic acid, (S) -spiro- [3,3] -heptane-2,6-carboxylic acid, (-)-camphanic acid and the like. Of these, (-)-camphoric acid, (+)-camphoric acid, (R) -spiro- [3,3] -heptane-2,6-carboxylic acid, (S) -spiro- [3,3]- Heptane-2,6-carboxylic acid and (-)-camphanic acid are preferred for obtaining good film properties.

These acid components having an asymmetric carbon moiety are used alone or in combination of two or more. The amount of the acid component having an asymmetric carbon moiety is usually 1 with respect to 100 parts by weight of the tetracarboxylic dianhydride having X ₁ and / or dicarboxylic acid and / or dicarboxylic acid component having an acid functional group. 1 to 40 parts by weight per type, and 1 to 50 parts by weight in total when combined. More preferably, it is good to mix | blend in 3-20 weight part.

Examples of the compound having a divalent to hexavalent organic group represented by Y ₁ in the general formula (1) include general diamines (having no acid functional group). Examples of the diamine include 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, 4,4′-diaminodiphenyl sulfide, m-phenylenediamine, and p-phenylenediamine. 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis (4-aminophenoxyphenyl) sulfone, bis (3-aminophenoxyphenyl) sulfone, bis (4-aminophenoxy) biphenyl, bis [4- (4 -Aminophenoxy) phenyl] ether, 1,4-bis (4-aminophenoxy) benzene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-diethyl-4,4'-diaminobiphenyl 3,3′-dimethyl-4,4′-diaminobiphenyl, 3,3′-di Tyl-4,4′-diaminobiphenyl, 2,2 ′, 3,3′-tetramethyl-4,4′-diaminobiphenyl, 2,2 ′, 3,3′-tetraethyl-4,4′-diaminobiphenyl 2,2′-dimethoxy-4,4′-diaminobiphenyl, 3,3′-dimethoxy-4,4′-diaminobiphenyl, 2,2′-di (trifluoromethyl) -4,4′-diaminobiphenyl Etc. These are used alone or in combination of two or more. In addition, the said diamine which can be used by this invention is not necessarily limited to what was mentioned here. Among these, 4,4'-diaminodiphenyl ether, m-phenylenediamine, p-phenylenediamine, bis (4-aminophenoxy) biphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'- Dimethyl-4,4′-diaminobiphenyl is preferred for obtaining good film properties with high heat resistance.

  Moreover, in order to adjust alkali solubility, the diamine which has an acid functional group which shows alkali solubility other than the said general diamine can be used. Examples of the diamine having an acid functional group include 2,4-diaminobenzoic acid, 3,5-diaminobenzoic acid, 3,3′-diaminobiphenyl-5,5′-dicarboxylic acid, and 4,4′-diamino. Diphenyl ether-5,5′-dicarboxylic acid, 4,4′-diaminodiphenylmethane-5,5′-dicarboxylic acid, 4,4′-diaminodiphenylsulfone-5,5′-dicarboxylic acid, 4,4′-diaminodiphenyl Those having one or more carboxyl groups such as sulfide-5,5′-dicarboxylic acid or isomers thereof; or 4,4′-diamino-2,2′-dihydroxybiphenyl, 4,4′-diamino- 3,3′-dihydroxybiphenyl, 2,2′-bis (3-amino-4-hydroxyphenyl) propane, 2,2′-bis (3-amino -4-hydroxyphenyl) hexafluoropropane, oxybis (3-amino-4-hydroxyphenyl), bis (3-amino-4-hydroxyphenyl) sulfone, 2,4-diaminophenol, 1,4-diamino-2, 5-dihydroxybenzene, N, N ′-(4-aminophenylcarbonyl) -3,3′-dihydroxybiphenyl, N, N ′-(3-aminophenylcarbonyl) -3,3′-dihydroxybiphenyl, N, N '-(4-aminophenylcarbonyl) 2,2'-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, N, N'-(3-aminophenylcarbonyl) 2,2'-bis (3- Amino-4-hydroxyphenyl) hexafluoropropane, N, N ′-(4-aminophenylcarbonyl) 2 2′-bis (3-amino-4-hydroxyphenyl) propane, N, N ′-(3-aminophenylcarbonyl) 2,2′-bis (3-amino-4-hydroxyphenyl) propane, N, N ′ -(4-aminophenylcarbonyl) -oxybis (3-amino-4-hydroxyphenyl), N, N '-(3-aminophenylcarbonyl) -oxybis (3-amino-4-hydroxyphenyl), N, N' -(4-aminophenylcarbonyl) -bis (3-amino-4-hydroxyphenyl) sulfone, N, N '-(3-aminophenylcarbonyl) -bis (3-amino-4-hydroxyphenyl) sulfone, N, N ′-(4-aminophenylcarbonyl) -2,4-diaminophenol, N, N ′-(3-aminophenylcarbonyl) -2,4- Diaminophenol, N, N ′-(4-aminophenylcarbonyl) -1,4-diamino-2,5-dihydroxybenzene, N, N ′-(3-aminophenylcarbonyl) -1,4-diamino-2, Examples thereof include those having a phenol group such as 5-dihydroxybenzene. These are used alone or in combination of two or more. The diamine having an acid functional group that can be used in the present invention is not necessarily limited to those listed here.

  Among the diamines having an acid functional group, 3,4-diaminobenzoic acid and 4,4′-diamino-3,3′-dihydroxybiphenyl having a phenol group, 2,2′-bis (3-amino-4- Hydroxyphenyl) propane, 2,2′-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, oxybis (3-amino-4-hydroxyphenyl), bis (3-amino-4-hydroxyphenyl) sulfone, 2,4-diaminophenol, 1,4-diamino-2,5-dihydroxybenzene, N, N ′-(4-aminophenylcarbonyl) -3,3′-dihydroxybiphenyl, N, N ′-(3-amino Phenylcarbonyl) -3,3′-dihydroxybiphenyl, N, N ′-(4-aminophenylcarbonyl) 2,2′-bi (3-amino-4-hydroxyphenyl) hexafluoropropane, N, N ′-(3-aminophenylcarbonyl) 2,2′-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, N, N ′ -(4-aminophenylcarbonyl) 2,2'-bis (3-amino-4-hydroxyphenyl) propane, N, N '-(3-aminophenylcarbonyl) 2,2'-bis (3-amino-4) -Hydroxyphenyl) propane, N, N '-(4-aminophenylcarbonyl) -oxybis (3-amino-4-hydroxyphenyl), N, N'-(3-aminophenylcarbonyl) -oxybis (3-amino- 4-hydroxyphenyl), N, N ′-(4-aminophenylcarbonyl) -bis (3-amino-4-hydroxyphenyl) Hong, N, N '- (3-aminophenyl-carbonyl) - bis (3-amino-4-hydroxyphenyl) sulfone is preferred for obtaining good alkali developing properties.

  A heat-resistant resin (resin component (1)) selected from the polyimide precursor or polybenzoxazole precursor having an asymmetric carbon, a copolymer of these two precursors, and a mixture of the two precursors. The asymmetric carbon in A)) can be introduced by using a diamine component having an asymmetric carbon moiety. Examples of the diamine component having an asymmetric carbon moiety include (R)-(+)-1,1-binaphthyl-2,2-diamine, (S)-(−)-1,1-binaphthyl-2,2 -Diamine, (+)-1,2-diphenyl-1,2-ethanediamine, (-)-1,2-diphenyl-1,2-ethanediamine and the like.

These diamine components having an asymmetric carbon moiety are used alone or in combination of two or more. The amount of the diamine component having an asymmetric carbon moiety is usually 1 to 20 parts by weight per 100 parts by weight with respect to 100 parts by weight of the diamine having Y ₁ and / or the acid functional group. In this case, the total amount is 1 to 30 parts by weight. More preferably, it is good to mix | blend in 3-20 weight part.

  The resin of the present invention is obtained by polymerizing these tetracarboxylic dianhydrides and / or general dicarboxylic acids and / or dicarboxylic acids having acid functional groups with general diamines and / or diamines having acid functional groups. A heat-resistant resin having an acidic functional group and / or a derivative substituent thereof as the component (A) can be obtained. For example, a polyimide precursor can be obtained by polymerizing a tetracarboxylic dianhydride and a general diamine and / or a diamine having an acid functional group. Further, a polybenzoxazole precursor can be obtained by polymerizing an activated esterified dicarboxylic acid and / or a dicarboxylic acid having an acid functional group and a diamine having a phenolic acid functional group. Furthermore, a tetracarboxylic dianhydride and / or a dicarboxylic acid and / or a dicarboxylic acid having an active esterified acid functional group and a diamine and / or a diamine having an acid functional group are copolymerized to obtain a polyimide / polybenzoic acid. An oxazole precursor copolymer can be obtained.

Control of solubility during development of the resin composition of the present invention by partially introducing a functional group such as a hydrogen atom represented by R ₁ in the general formula (1) or an organic group having 1 to 20 carbon atoms. And / or pattern processing utilizing photoreaction is possible. Examples of the functional group include methyl, ethyl, propyl, isopropyl, n-butyl, s-butyl, t-butyl, cyclopropenyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexylmethyl, cyclohexenyl, norbornyl, norbornenyl, adamantyl, Benzyl, p-nitrobenzyl, trifluoromethyl, methoxyethyl, ethoxyethyl, methoxymethyl, ethoxymethyl, methoxyethoxymethyl, benzoxymethyl, tetrahydropyranyl, ethoxytetrahydropyranyl, tetrahydrofuranyl, 2-trimethylsilylethoxymethyl, trimethylsilyl , T-butyldimethylsilyl, 3-oxocyclohexyl, 9-fluorenylmethyl, methylthiomethyl, allyl alcohol, 2-methyl-2-propyl Pen-1-ol, crotyl alcohol, 3-buten-1-ol, 3-buten-2-ol, 3-methyl-2-buten-1-ol, 2-methyl-3-buten-1-ol, 3-methyl-3-buten-1-ol, 2-methyl-3-buten-2-ol, 2-penten-1-ol, 4-penten-1-ol, 3-penten-2-ol, 4- Penten-2-ol, 1-penten-3-ol, 4-methyl-3-penten-1-ol, 3-methyl-1-penten-3-ol, 2-hexen-1-ol, 3-hexene -1-ol, 4-hexen-1-ol, 5-hexen-1-ol, 1-hexen-3-ol, 1-heptane-3-ol, 6-methyl-5-heptan-2-ol, -Octane-3-ol, citronellol, 3-nonen-1-ol, 5-decane-1 Ol, 9-decan-1-ol, 7-decan-1-ol, 1,4-pentadien-3-ol, 2,4-hexadien-1-ol, 1,5-hexadien-3-ol, 1, 6-heptadiene-4-ol, 2,4-dimethyl-2,6-heptadien-1-ol, nerol, geraniol, linalool, 2-cyclohexen-1-ol, 3-cyclohexene-1-methanol, isopulegol, 5- Norbornene-2-ol, 5-norbornene-2-methanol, ethylene glycol vinyl ether, 1,4-butanediol vinyl ether, 1,6-hexanediol vinyl ether, diethylene glycol vinyl ether, 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 2 -Hydroxyethyl methacrylate, 3- Hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, pentaerythritol diacrylate monostearate, pentaerythritol triacrylate, caprolactone 2- (methacryloyloxy) ethyl ester, dicaprolactone 2- (methacryloyloxy) ethyl Examples thereof include esters, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate and the like. The functional groups that can be used in the present invention are not necessarily limited to those listed here. By partially introducing these functional groups, the alkali solubility of the resin composition of the present invention can be controlled. Moreover, when it has an acidic functional group at the terminal of the polymer which comprises the said resin component (A), it is also possible to introduce | transduce these acidic functional groups.

  Among the above specific functional groups, methyl, ethyl, propyl, isopropyl, n-butyl, s-butyl, t-butyl, methoxyethyl, ethoxyethyl, methoxymethyl, ethoxymethyl, methoxyethoxymethyl, tetrahydropyranyl, ethoxy Tetrahydropyranyl and tetrahydrofuranyl are preferred for favorably controlling the solubility of the resin composition of the present invention.

In addition, by introducing into the R ₂ in the general formula (1) a functional group of the same type as the functional group that can be introduced into the R ₁ in the general formula (1), the resin composition of the present invention It becomes possible to control solubility during development and / or pattern processing utilizing photoreaction. Moreover, alkali solubility of the resin composition of the present invention can be controlled by partially introducing these functional groups. Furthermore, when an acidic functional group is present at the terminal of the polymer constituting the resin component (A), it is possible to introduce these acidic functional groups.

  Further, the resin component (A) of the present invention is a polymer having an amine functional group and / or a derived substituent thereof, an acidic functional group and / or a derived substituent thereof, or at least one of them, that is, , Any of polymers in which the functional group and the substituent are combined as a terminal group. When the amine functional group at the terminal is a primary amine, the stability of the photosensitive resin composition deteriorates due to side reactions, so at least one of the two hydrogen atoms on the amine functional group is another atom or other atom. Substitution with a functional group is preferred for obtaining stability as a photosensitive resin composition. The substitution ratio is more preferably in the range of 30% to 100% in order to obtain sufficient stability.

  Examples of substituents on nitrogen derived from the amine functional group include hydrogen, amide, imide, carbamate, sulfonyl, sulfenyl, phosphinyl, alkylsilyl and the like. Of these, amide, imide, carbamate, and sulfonyl are preferable in terms of obtaining more excellent cured resin properties. These substituents are represented by the following general formulas (2) to (5).

（各式中、Ｒ₃は１価の有機基であり、炭素原子数は１〜２０のものが好ましい。式（３）中において、Ｘ₃は酸素、硫黄もしくは窒素原子であり、Ｘ₃が酸素原子もしくは硫黄原子の場合はｎ＝１、窒素原子の場合はｎ＝２である。）

(In each formula, R ₃ is a monovalent organic group and preferably has 1 to 20 carbon atoms. In formula (3), X ₃ is an oxygen, sulfur or nitrogen atom, and X ₃ is (In the case of an oxygen atom or a sulfur atom, n = 1, and in the case of a nitrogen atom, n = 2.)

Examples of R ₃ include methyl, ethyl, propyl, isopropyl, n-butyl, s-butyl, t-butyl, cyclopropenyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexylmethyl, cyclohexenyl, norbornyl, norbornenyl, adamantyl, Benzyl, p-nitrobenzyl, trifluoromethyl, methoxyethyl, ethoxyethyl, methoxymethyl, ethoxymethyl, methoxyethoxymethyl, benzoxymethyl, ethoxytetrahydropyranyl, tetrahydrofuranyl, 2-trimethylsilylethoxymethyl, trimethylsilyl, t-butyl Examples include, but are not necessarily limited to, dimethylsilyl, 3-oxocyclohexyl, 9-fluorenylmethyl, methylthiomethyl and the like.

As the acidic functional group and / or a derivative substituent thereof, those represented by R ₁ and R ₂ in the above general formula (1) are used.

(Photoreactive compound (B))
The photoreactive compound (B) used in the resin composition of the present invention is a photosensitizer and has a property of generating an acid when irradiated with light. The light of the resin composition of the present invention It is a component that fulfills the function of increasing the solubility in an alkaline aqueous solution in the irradiated part. Examples of the type include o-quinonediazide compounds, aryldiazonium salts, diaryliodonium salts, triarylsulfonium salts, and the like. The compounds are not limited to those listed here, and any compound that generates an acid by light can be used.

  The o-quinonediazide compound can be obtained, for example, by subjecting o-quinonediazidesulfonyl chlorides to a hydroxy compound, an amino compound or the like in the presence of a dehydrochlorinating agent.

  Examples of the o-quinonediazide sulfonyl chlorides include benzoquinone-1,2-diazide-4-sulfonyl chloride, naphthoquinone-1,2-diazide-5-sulfonyl chloride, and naphthoquinone-1,2-diazide-4-sulfonyl chloride. Can be used, but are not necessarily limited to those listed here.

  The compound to be reacted with the o-quinonediazide sulfonyl chloride is preferably a hydroxy compound from the viewpoint of photosensitive properties. Examples of the hydroxy compound include hydroquinone, resorcinol, pyrogallol, bisphenol A, bis (4-hydroxyphenyl) methane. 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 2,3,4-trihydroxybenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, 2,2 ′, 4,4′-tetra Hydroxybenzophenone, 2,3,4,2 ′, 3′-pentahydroxybenzophenone, 2,3,4,3 ′, 4 ′, 5′-hexahydroxybenzophenone, bis (2,3,4-trihydroxyphenyl) Methane, bis (2,3,4-trihydroxyphene Propane, 4b, 5,9b, 10-tetrahydro-1,3,6,8-tetrahydroxy-5,10-dimethylindeno [2,1-a] indene, tris (4-hydroxyphenyl) methane, Tris (4-hydroxyphenyl) ethane or the like can be used. Such hydroxy compounds are not necessarily limited to those listed here.

  Examples of the aryldiazonium salt, diaryliodonium salt, triarylsulfonium salt include benzenediazonium-p-toluenesulfonate, diphenyliodonium 9,10-dimethoxyanthracene-2-sulfonate, and tris (4-t-butylphenyl). ) Sulfonium trifluoromethanesulfonate, N-naphthalimide trifluoromethanesulfonate, p-nitrobenzyl-9,10-dimethoxyanthracene-2-sulfonate, 4-methoxy-α-[[[(4-methylphenyl) sulfonyl] oxy] Imino] benzeneacetonitrile, 2- (2′-furylethenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine and the like can be used. Such aryldiazonium salts, diaryliodonium salts, triarylsulfonium salts and the like are not necessarily limited to those listed here.

  These photosensitizers (B) are used alone or in combination of two or more. The amount of the photosensitizer (B) used is usually 0.1 to 40 parts by weight per 100 parts by weight of the resin component (A), and 0.1 to 40 parts by weight in total when combined. The More preferably, it is good to mix | blend in the range of 1-20 weight part.

  Examples of the solvent (C) in the present invention include gamma butyrolactone, N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylsulfoxide, hexamethylphosphortriamide, dimethyl Polar solvents such as imidazolidinone and N-acetyl-ε-caprolactam are preferable. Besides these polar solvents, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons, and more Specifically, for example, acetone, diethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, diethyl malonate, diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl Ether, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichloro butane, trichloroethane, chlorobenzene, o- dichlorobenzene, hexane, heptane, octane, benzene, toluene, and xylene can be used. These organic solvents are used alone or in combination of two or more. However, the solvent (C) that can be used in the present invention is not particularly limited as long as it dissolves the components of the photosensitive resin composition of the present invention.

(Other ingredients)
In addition to the components (A), (B), and (C), a silane coupling agent may be added to the photosensitive resin composition of the present invention as an adhesion enhancer for a silicon substrate. Further, instead of mixing an adhesion enhancer as an additive component, the resin component (A) is modified using diaminosiloxane as a diamine that becomes a raw material constituting the Y part in the general formula (1), thereby The adhesion to the silicon substrate can also be enhanced.

  As the silane coupling agent, alkoxysilanes are preferable from the viewpoint of reactivity. For example, vinyltrimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyltrimethoxysilane, 3-aminopropyltrimethoxysilane. N-methylaminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxy Silane, N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propanamine, N, N-bis (3- (trimethoxysilyl) propyl) ethylenediamine, N- (3-tri Methoxysilylpropyl) pyrrole, ureido Examples include propyltrimethoxysilane, (3-triethoxysilylpropyl) -t-butylcarbamate, N-phenylaminopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, (furfuryloxymethyl) triethoxysilane, and the like. It is done.

  Further, as other components, a dissolution accelerator can be used for the purpose of increasing the contrast. Examples of the dissolution accelerator include compounds containing an acidic functional group, and the acidic functional group is preferably a phenolic hydroxyl group, a carboxylic acid group, or a sulfonic acid group. Examples of the dissolution accelerator having an acidic functional group include methylene bisphenol, 2,2-methylene bis (4-methylphenol), 4,4-oxybisphenol, and 4,4- (1-methylethylidene) bis (2- Methylphenol), 4,4- (1-phenylethylidene) bisphenol, 5,5- (1-methylethylidene) bis (1,1- (biphenyl) -2-ol), 4,4,4-ethylidenetris Phenol, 2,6-bis ((2-hydroxy-5-methylphenyl) methyl) -4-methylphenol, 4,4- (1- (4- (1- (4-hydroxyphenyl) -1-methylethyl) ) Phenyl) ethylidene) bisphenol, 4,4-sulfonyldiphenol, (2-hydroxy-5-methyl) -1,3-benzenedimethylol, , 3-methylenebis (2-hydroxy-5-methylbenzenemethanol), salicylic acid, malonic acid, glutaric acid, 2,2-dimethylglutaric acid, maleic acid, diglycolic acid, 1,1-cyclobutanedicarboxylic acid, 3,3 -Tetramethylene glutaric acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-adamantanedicarboxylic acid, 1,2-phenylenedioxydiacetic acid, 1,3-phenylenediacetic acid, 1, Examples include 4-phenylenediacetic acid, terephthalic acid, isophthalic acid, 4,4′-oxydiphenyldicarboxylic acid, 4,4-biphenyldicarboxylic acid, 4-hydroxybenzenesulfonic acid, and the like. These dissolution promoters are used alone or in combination of two or more.

  Furthermore, as other additive components, an addition polymerizable compound, a dissolution inhibitor, a stabilizer and the like may be blended depending on the purpose.

(Formation of patterned insulating cured film)
The photosensitive resin composition of the present invention was formed by being applied onto a substrate such as a silicon wafer, a metal substrate, or a ceramic substrate by a dipping method, a spray method, a screen printing method, a spin coating (spin coating) method, or the like. By suitably heating and drying the coating film, the solvent can be evaporated to obtain a coating film having no tackiness. Actinic rays or actinic rays are irradiated onto the coating film through a mask on which a desired pattern is drawn. As actinic rays or actinic rays to be irradiated, contact / proximity exposure machines using an ultrahigh pressure mercury lamp, mirror projection exposure machines, i-line steppers, g-line steppers, other ultraviolet rays, visible light sources, X-rays, and electron beams be able to. Thereafter, a post-exposure bake (PEB) treatment is performed as necessary, followed by development. In the part of the coating film irradiated with actinic rays, acid is generated from the photoreactive compound (B) contained as a component, and the part becomes soluble in the developer. After irradiating with actinic rays, the coating film is patterned into a desired pattern by dissolving and removing the irradiated portion with a developer.

  As the developer, an organic solvent or an alkaline aqueous solution is used. Organic solvent developers include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, hexamethylphosphoric triamide, γ-butyrolactone, water, or alcohol , Ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons, more specifically, for example, methanol, ethanol, isopropyl alcohol, acetone, diethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, Cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, diethyl malonate, diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, dichloromethane, , 2-dichloroethane, 1,4-dichloro butane, trichloroethane, chlorobenzene, o- dichlorobenzene, hexane, heptane, octane, benzene, toluene, xylene and the like are used alone or in combinations of two or more.

  Examples of the alkaline aqueous solution used as a developer include aqueous solutions of alkali metal hydroxides such as caustic potash and caustic soda, quaternary ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, ethanolamine, propylamine, ethylenediamine, etc. An aqueous amine solution is used.

  After development, rinsing is performed with water or a poor solvent as necessary. For example, methanol, ethanol, isopropyl alcohol, benzene, toluene, xylene, methyl cellosolve, water or the like is used as the rinse liquid.

  By heating the pattern obtained by the above development, a patterned cured film of stable high heat resistant polyimide or polybenzoxazole from which the photosensitizer and the solvent are removed is obtained.

  The heating temperature at this time is preferably 150 to 500 ° C, and more preferably 200 to 400 ° C. Even if this heating temperature is less than 150 ° C., or conversely exceeds 500 ° C., the mechanical properties and thermal properties of the film tend to deteriorate. Moreover, it is preferable that the heating time at this time shall be 0.05 to 10 hours. Even if the heating time is less than 0.05 hours, or conversely exceeds 10 hours, the mechanical properties and thermal properties of the film tend to deteriorate.

  Next, an example of the manufacturing process of the semiconductor device of the present invention will be described with reference to the drawings. FIG. 1 is a manufacturing process diagram of a semiconductor device having a multilayer wiring structure. From the top to the bottom, a series of steps from the first step (a) to the fifth step (e) is shown.

  In FIG. 1, a semiconductor substrate 1 such as a Si substrate having circuit elements is covered with a protective film 2 such as a silicon oxide film except for a predetermined portion of the circuit elements, and a first conductor layer 3 is formed on the exposed circuit elements. Has been. A resin composition solution for an interlayer insulating film is applied onto the semiconductor substrate 1 by a spin coat method or the like to form a coating film, and this coating film is appropriately heated and dried to form an interlayer insulating film layer 4 ( First step (a)). The photosensitive resin composition of the present invention can also be used as the resin composition for the interlayer insulating film.

  Next, a pattern mask layer 5 is formed on the interlayer insulating film layer 4 by spin coating or the like. The pattern mask layer 5 is provided with a window 6A so that a predetermined portion of the interlayer insulating film 4 is exposed by a known photolithography technique (second step (b)). Actinic rays or actinic rays are irradiated through the pattern mask. After the irradiation, the interlayer insulating film layer 5 is heat-treated, and then the window 6A portion is dissolved and removed with an alkali developer to open the window 6B in the interlayer insulating film layer 5. Next, only the pattern mask layer 5 is completely removed without damaging the first conductor layer 3 (third step (c)).

  Further, the second conductor layer 7 is formed by using a known photolithography technique, and electrical connection with the first conductor layer 3 is realized through the window 6B (fourth step (d)). When a multilayer wiring structure having three or more layers is formed, each layer can be formed by repeating the above steps.

  Next, the surface protective film layer 8 is formed. This surface protective film is formed using the photosensitive resin composition liquid of the present invention. That is, the photosensitive resin composition liquid of the present invention is applied onto the interlayer insulating film layer 5 and the second conductor layer 7 by spin coating, the coating film is heated and dried, and a pattern mask is applied to the dried coating film. Then, the exposed portion is selectively exposed, and the exposed portion is dissolved and removed with an alkali developer to form the window 6C. Thereafter, the dried coating film is cured by heating to obtain the surface protective film layer 8 (fifth step (e)).

  Since the photosensitive resin composition of the present invention has good insulating properties and mechanical properties, and also has excellent photosensitive properties, as described above, in the production of semiconductor devices, the interlayer insulating film layer and the surface By using the resin composition of the present invention for an insulating portion such as a protective film layer, an insulating portion having a certain quality can be formed easily and at low cost. As a result, by manufacturing a semiconductor device using the resin composition of the present invention, a high-quality semiconductor device having excellent insulating characteristics and mechanical characteristics can be provided at a lower cost.

  Hereinafter, the present invention will be described in more detail with reference to examples. The following examples are only suitable examples for explaining the present invention, and do not limit the present invention.

(Synthesis Example 1: Preparation of resin component (A) of the present invention)
Cool a solution of 100 g dry N-methylpyrrolidone and 20.6 g (0.08 mol) 4,4′-oxybis (carboxyphenyl) in a closed reaction vessel equipped with stirrer, thermometer and nitrogen inlet tube to 0 ° C. Then, 19.1 g (0.16 mol) of thionyl chloride was added dropwise and stirred for 30 minutes after the addition to obtain a reaction solution (R-1).

  Then, in another sealed reaction vessel equipped with a stirrer, thermometer and nitrogen inlet tube, 100 g dry N-methylpyrrolidone and 40.3 g (0.11 mol) 2,2-bis (3-amino-4). -Hydroxyphenyl) hexafluoropropane and a solution of 1.58 g (0.02 mol) of pyridine are injected and cooled to 0 ° C., to which 2.09 g (0.02 mol) of cyclopropanecarbonyl chloride is added. After dropping, the mixture was stirred at room temperature for 30 minutes. Further, 15.82 g (0.2 mol) of pyridine was added and cooled to 0 ° C., and then 4.33 g (0.02 mol) of (+)-camphoric acid chloride (acid component having an asymmetric carbon moiety) was added. Further, the reaction solution (R-1) obtained earlier was added dropwise over 30 minutes and stirred at room temperature for 30 minutes. The reaction mixture was treated with 2.0 liters of ion exchange water with vigorous stirring. The precipitated solid was further washed with ion-exchanged water, sucked and dried on a filtration filter, and dried under reduced pressure at room temperature until the water content was less than 1.0% by weight. -1) (resin component (A)) was obtained. The polymer (A-1) having this asymmetric carbon had a weight average molecular weight of 22,200 and a dispersion of 1.8.

(Synthesis Example 2: Preparation of resin component (A) of the present invention)
100 g of dry N-methylpyrrolidone and 13.3 g (0.18 mol) of n-butanol in a closed reaction vessel equipped with a stirrer, a thermometer and a nitrogen inlet tube were added, and 27.9 g (0.09 mol) of bis ( 3,4-Dicarboxyphenyl) ether dianhydride was added and stirred at 70 ° C. for 24 hours to obtain an ester. This solution was cooled to 0 ° C., 21.4 g (0.18 mol) of thionyl chloride was added dropwise, and the mixture was stirred for 30 minutes after the addition to obtain a reaction solution (R-2).

  Then, in a separate sealed reaction vessel equipped with a stirrer, thermometer and nitrogen inlet tube, 100 g dry N-methylpyrrolidone and 33.0 g (0.09 mol) 2,2-bis (3-amino-4-). Hydroxyphenyl) hexafluoropropane and 15.82 g (0.2 mol) of pyridine were added and dissolved by stirring. This solution was cooled to 0 ° C., 2.17 g (0.01 mol) of (−)-camphanic acid chloride (acid component having an asymmetric carbon moiety) was added, and the reaction solution (R— 2) was added dropwise over 30 minutes and then stirred at room temperature for 30 minutes. The reaction mixture was treated with 2.0 liters of ion exchange water with vigorous stirring. The precipitated solid was further washed with ion-exchanged water, sucked and dried on a filtration filter, and dried under reduced pressure at room temperature until the water content was less than 1.0% by weight. -2) (resin component (A)) was obtained. The polymer (A-2) having this asymmetric carbon had a weight average molecular weight of 22,900 and a dispersion of 1.65.

(Synthesis Example 3: Preparation of comparative resin component)
Cool a solution of 100 g dry N-methylpyrrolidone and 25.8 g (0.1 mol) 4,4′-oxybis (carboxyphenyl) in a closed reaction vessel equipped with a stirrer, thermometer and nitrogen inlet tube to 0 ° C. 23.8 g (0.2 mol) of thionyl chloride was added dropwise and stirred for 30 minutes after the addition to obtain a reaction solution (R-1).

  Then, in another sealed reaction vessel equipped with a stirrer, thermometer and nitrogen inlet tube, 100 g dry N-methylpyrrolidone and 40.3 g (0.11 mol) 2,2-bis (3-amino-4). -Hydroxyphenyl) hexafluoropropane and a solution of 1.58 g (0.02 mol) of pyridine are injected and cooled to 0 ° C., to which 2.09 g (0.02 mol) of cyclopropanecarbonyl chloride is added. After dropping, the mixture was stirred at room temperature for 30 minutes. Further, 15.82 g (0.2 mol) of pyridine was added and cooled to 0 ° C., and then the reaction solution (R-1) obtained earlier was added dropwise over 30 minutes and stirred at room temperature for 30 minutes. The reaction mixture was treated with 2.0 liters of ion exchange water with vigorous stirring. The precipitated solid was further washed with ion-exchanged water, sucked and dried on a filtration filter, and dried under reduced pressure at room temperature until the water content was less than 1.0% by weight. Resin component). This polymer (P-1) had a weight average molecular weight of 23,900 and a dispersion of 1.71.

(Synthesis Example 4: Preparation of Comparative Resin Component)
100 g of dry N-methylpyrrolidone and 14.8 g (0.2 mol) of n-butanol in a closed reaction vessel equipped with a stirrer, a thermometer and a nitrogen introduction tube were placed, and 31.0 g (0.1 mol) of bis ( 3,4-Dicarboxyphenyl) ether dianhydride was added and stirred at 70 ° C. for 24 hours to obtain an ester. The solution was cooled to 0 ° C., 23.8 g (0.2 mol) of thionyl chloride was added dropwise, and the mixture was stirred for 30 minutes after the addition to obtain a reaction solution (R-2).

  Then, in another sealed reaction vessel equipped with a stirrer, thermometer and nitrogen inlet tube, 100 g dry N-methylpyrrolidone and 33.0 g (0.09 mol) 2,2-bis (3-amino-4) -Hydroxyphenyl) hexafluoropropane and 15.82 g (0.2 mol) of pyridine were added and dissolved by stirring. This solution was cooled to 0 ° C., and the reaction solution (R-2) obtained earlier was added dropwise over 30 minutes, followed by stirring at room temperature for 30 minutes. The reaction mixture was treated with 2.0 liters of ion exchange water with vigorous stirring. The precipitated solid was further washed with ion-exchanged water, sucked and dried on a filtration filter, and dried under reduced pressure at room temperature until the water content was less than 1.0% by weight. Resin component). This polymer (P-2) had a weight average molecular weight of 24,100 and a dispersion of 1.69.

(Synthesis Example 5: Preparation of photoreactive compound (B))
14.6 g (0.05 mol) of tris (4-hydroxyphenyl) methane and 37.6 g of naphthoquinone-1,2-diazido-5-sulfonyl chloride in a closed reaction vessel equipped with a stirrer, a thermometer and a nitrogen introduction tube (0 .14 mol) and 200 g of dry N-methylpyrrolidone solution, 14.2 g (0.14 mol) of triethylamine was reacted dropwise with cooling. The reaction mixture was filtered, and the filtrate was subjected to 2.0 liters of ion exchange. Treated with water with vigorous stirring. The precipitated solid was further washed with ion-exchanged water, sucked and dried on a filtration filter, and dried under reduced pressure at room temperature until the water content was less than 1.0% by weight, to give an orthoquinonediazide compound (B-1). (Photoreactive compound (B)) was obtained.

(Example 1)
(Preparation of photosensitive resin composition and production of pattern cured film)
In a three-necked flask equipped with a stirrer, a thermometer, and a nitrogen inlet tube, the resin component (A) obtained in (Synthesis Example 1): 10 g of polymer (A-1) having asymmetric carbon and γ-butyrolactone (solvent (C)) After stirring and mixing 15 g to dissolve the polymer, 1.0 g of the photoreactive compound (B): photosensitive agent (B-1) obtained in (Synthesis Example 5) was further added, and the mixture was stirred overnight at room temperature. After dissolution, the mixture was filtered and a photosensitive resin composition solution was obtained. This solution was spin-coated on a 5-inch silicon wafer and then dried to form a 5.0 ± 1.0 μm coating film. A resist pattern film (pattern mask) was formed on the obtained coating film and exposed using an i-line stepper with an exposure dose of 200 to 1000 mJ / cm ² . This was left in a light-shielding box for 1 hour, and then developed with a paddle using a 2.38% tetramethylammonium hydroxide aqueous solution (alkali developer). As a result, the resolution reached 10 μm (minimum line width) at an exposure amount of 800 mJ / cm ² , and a good relief pattern (patterned cured film) was obtained.

(Evaluation of cured film)
The photosensitive resin composition solution was spin-coated on a 5-inch silicon wafer and then dried to form a 15.0 ± 1.0 μm coating film. A contact aligner was used on the obtained coating film to form a pattern. A mask was formed and exposed at an exposure amount of 1500 mJ / cm ² . This was left in a light-shielding box for 1 hour, and then paddle developed using a 2.38% tetramethylammonium hydroxide aqueous solution to obtain a 10 mm × 80 mm strip-shaped patterned film. This wafer was baked at 300 ° C. for 1 hour in an oven purged with nitrogen to obtain a cured film. After stripping the strip-shaped thin film from the silicon wafer using a hydrofluoric acid aqueous solution and drying, the elongation of the cured film was measured using an autograph. As a result, the elongation percentage of the cured film was 40%.

(Example 2)
(Preparation of photosensitive resin composition and production of pattern cured film)
As a blend, resin component (A) obtained in Synthesis Example 2: 10 g of polymer (A-2) having asymmetric carbon, 15 g of γ-butyrolactone (solvent (C)), and photoreactivity obtained in Synthesis Example 5 Compound (B): 1.0 g of the photosensitizer (B-1) was used, and the rest was processed in the same manner as in Example 1, but the resolution was up to 10 μm (minimum line width) at an exposure amount of 700 mJ / cm ^2. And a good relief pattern film was obtained.

(Evaluation of cured film)
Moreover, the elongation rate was measured for the strip-shaped cured film obtained by processing similar to Example 1 using the autograph. As a result, the elongation percentage of the cured film was 34%.

(Comparative Example 1)
(Preparation of photosensitive resin composition and production of pattern cured film)
Comparative resin components obtained in Synthesis Example 3 as a blend: 10 g of polymer (P-1) and 15 g of γ-butyrolactone (solvent (C)) and photoreactive compound (B) obtained in Synthesis Example 5: photosensitive When 1.0 g of the agent (B-1) was used, and the other treatment was performed in the same manner as in Example 1, the resolution reached 20 μm (minimum line width) at an exposure amount of 1000 mJ / cm ^2. Obtained.

(Evaluation of cured film)
Moreover, the elongation rate was measured for the strip-shaped cured film obtained by processing similar to Example 1 using the autograph. As a result, the elongation percentage of the cured film was 12%.

(Comparative Example 2)
(Preparation of photosensitive resin composition and production of pattern cured film)
As a blend, the resin component obtained in Synthesis Example 4: 10 g of polymer (P-2) and 15 g of γ-butyrolactone (solvent (C)) and the photoreactive compound (B) obtained in Synthesis Example 5: photosensitizer ( When B-1) was used in the same manner as in Example 1 except that 1.0 g was used, the resolution reached 20 μm (minimum line width) at an exposure amount of 1200 mJ / cm ² , and a relief pattern film was obtained. It was.

(Evaluation of cured film)
Moreover, the elongation rate was measured for the strip-shaped cured film obtained by processing similar to Example 1 using the autograph. As a result, the elongation percentage of the cured film was 9%.

  As is clear from the examples and comparative examples, the photosensitive resin composition according to the present invention having an asymmetric carbon moiety in the resin component is a comparative example having a resin component not having an asymmetric carbon moiety. It can be seen that, compared with the photosensitive resin composition, the photosensitive properties are remarkably excellent, and the mechanical properties of the resulting cured film are also significantly improved.

  The resin composition of the present invention has, as a resin component, a heat-resistant resin comprising a photosensitive polyimide precursor, a polybenzoxazole precursor, a copolymer thereof, or a mixture thereof that realizes excellent cured resin properties. The resin component has an asymmetric carbon moiety. With such a characteristic configuration, the resin composition according to the present invention has excellent photosensitive properties, and can form a cured film having good insulating properties and mechanical properties. Therefore, if the insulating part of a semiconductor device is formed using the photosensitive resin composition according to the present invention, a semiconductor device having excellent insulating characteristics and mechanical characteristics can be provided at a lower cost.

It is a manufacturing process figure of the semiconductor device of a multilayer wiring structure.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Semiconductor substrate 2 ... Protective film 3 ... 1st conductor layer 4 ... Interlayer insulating film layer 5 ... Photosensitive resin layer 6A, 6B, 6C ... Window 7 ... 2nd conductor layer 8 ... Surface protective film layer

Claims (3)

A photosensitive resin composition comprising a resin component (A), a photoreactive compound (B) that generates an acid by photoreaction, and a solvent (C),
The resin component (A) has an asymmetric carbon moiety and has the following general formula (1):

Wherein X ₁ is a divalent to tetravalent organic group, Y ₁ is a divalent to hexavalent organic group, p and q are 0 or an integer of 1 to 4, and R ₁ is a hydrogen atom or an organic group having 1 to 20 carbon atoms. And l and m are 0 or an integer from 1 to 2 and n is an integer from 2 to 1000, provided that R ₁ is hydrogen or a monovalent organic group. A photosensitive resin comprising a heat-resistant resin comprising at least one selected from a polyimide precursor or a polybenzoxazole precursor, a copolymer of these two precursors, and a mixture of the two precursors Composition.   The photosensitive resin composition according to claim 1, wherein the photoreactive compound (B) is a compound that generates a carboxyl group by a photoreaction.   A semiconductor device using the photosensitive resin composition according to claim 1.

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